KR20140058437A - Resin composition for sealing electrical and electronic parts, method for producing sealed electrical and electronic parts, and sealed electrical and electronic parts - Google Patents

Abstract

An object of the present invention is to provide a resin composition for sealing electrical and / or electronic parts capable of providing flame-retardant electrical and / or electronic parts encapsulant without filling-up of a practical level of a sealing agent and no bleeding out of the flame retardant while maintaining adhesiveness between the encapsulant and the electric / And the like. The present invention relates to a thermosetting resin composition comprising a copolymer polyester elastomer (X), a brominated epoxy resin (B1), a non-brominated epoxy resin (B2) and a polyolefin resin (C) And having a melt viscosity of not less than 5 dPa · s and not more than 3000 dPa · s when extruded from a die having a pore diameter of 1.0 mm and a thickness of 10 mm and an electrical and electronic parts- And a manufacturing method of the component sealing member.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for sealing an electrical and / or electronic part, a method of manufacturing an electrical / electronic part sealing body, and a sealing body for electrical / electronic parts,

TECHNICAL FIELD The present invention relates to a sealing member for electrical and electronic parts sealed by a resin composition, a method for producing the sealing member, and a resin composition suitable for such use.

BACKGROUND ART Electric and electronic parts widely used in automobiles and telephone (electrification) products require electrical insulation from the outside in order to achieve their intended use, A sealing method is required. Since the hot-melt resin which can be sealed only by heating and melting can be solidified only by cooling after sealing, a sealing member is formed, so that the productivity is high and the member can be easily recycled by heating and melting the resin. And is suitable for sealing electric and electronic parts.

Polyesters having both electrical insulation and water resistance are considered to be very useful materials for this application. In general, injection molding at a high pressure of several hundred MPa or more is required in order to seal parts having complicated shapes with high melt viscosity, The parts may be destroyed. On the other hand, Patent Document 1 discloses a polyester resin composition for molding containing a polyester resin having a specific composition and physical properties and an antioxidant, and it has been disclosed that sealing at a low pressure without damaging electrical and electronic parts is possible have. With this resin composition, it is possible to obtain a molded article having a good initial adhesion property, and it becomes possible to apply a polyester resin composition to general electric / electronic parts. Patent Document 2 discloses a resin composition for sealing electric / electronic parts in which a crystalline polyester resin, an epoxy resin, and a polyolefin resin are blended. This composition has a high initial bonding strength to a polybutylene terephthalate plate containing 30% by weight of a glass epoxy or glass filler, and has a high heat load of 1000 cycles at a temperature of -40 ° C and 80 ° C, a temperature of 85 ° C and 85% The decrease in the adhesion strength due to the time load and the load at 105 ° C for 1000 hours was also suppressed.

Patent Document 1: Japanese Patent No. 3553559 Patent Document 2: JP-A-2010-150471

In some cases, flame retardancy is required for the electrical and electronic parts encapsulating material. However, it is described in Patent Documents 1 and 2 that a flame retardant can be incorporated, and no specific flame retardant prescription has been proposed. In order to impart flame retardancy to the electrical and electronic component encapsulating material, a flame retardant may be added. However, when a conventional flame retardant is added, it is necessary to blend the flame retardant with a high blending ratio in order to obtain practical flame retardancy. It has been proved that problems such as poor chargeability of the sealing agent, deterioration of the adhesiveness between the sealing agent and the electric / electronic part, and bleeding out of the flame retardant are caused. Disclosure of the Invention Problem to be solved by the Invention It is an object of the present invention to provide a flame-retardant electrical and / or electronic parts encapsulating material capable of providing a flame-retardant electrical-electronic part encapsulating material having a filling property of a practical- To provide a resin composition.

(1) A polyester resin composition comprising (1) a copolymer polyester elastomer (X), a brominated epoxy resin (B1), a brominated epoxy resin (B2) and a polyolefin resin (C) And has a melt viscosity of not less than 5 dPa · s and not more than 3.0 × 10 ³ dPa · s when extruded from a die having a pore diameter of 1.0 mm and a thickness of 10 mm.

(2) A composition comprising a crystalline polyester resin (A), a brominated epoxy resin (B1), a non-brominated epoxy resin (B2) and a polyolefin resin (C) in which a polyether diol is copolymerized and dried to a moisture content of 0.1% And a melt viscosity of 5 dPa 占 퐏 or more and 3000 dPa 占 퐏 or less when extruded from a die having a pore diameter of 1.0 mm and a thickness of 10 mm by heating at 220 占 폚 and applying a pressure of 1 MPa.

(3) The resin for sealing electric / electronic parts according to (1) or (2), wherein the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) are both bisphenol A type or novolac type epoxy resins Composition.

(4) 100 parts by mass of the copolymerized polyester elastomer (X) or the crystalline polyester resin (A), 5 to 100 parts by mass of the total of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) and the polyolefin resin (C) (1) to (3), wherein 0.1 to 100 parts by mass of the non-brominated epoxy resin (B2) is contained in an amount of 10 to 50% by mass of the brominated epoxy resin (B1) Resin composition for sealing.

(5) The resin composition for sealing electric / electronic parts according to any one of (1) to (4), further comprising a phenol resin and / or a phenol-modified alkylbenzene resin (D).

(6) The resin composition as described in any one of (1) to (5) above is heated and kneaded, and then the resin composition is heated to a temperature of not less than 130 ° C. and not more than 260 ° C. and a resin composition pressure of not less than 0.1 MPa Wherein the sealing material is injected at 10 MPa or less.

(7) An electric / electronic part sealing member sealed with the resin composition as described in any one of (1) to (5).

By using the resin composition for encapsulating electric / electronic parts of the present invention as a sealing material in an electric / electronic part sealing material, it is possible to improve the filling property of a practical level sealing material and the bleeding out of the flame retardant while maintaining the adhesiveness between the sealing material and the electric / It is possible to obtain a flame-retardant electrical and electronic parts-sealing member.

1 is a schematic diagram showing a method of preparing a test piece for adhesion strength test.
2 is a schematic diagram showing a method of preparing a test piece for adhesion strength test.
3 is a schematic diagram showing a method for preparing a test piece for adhesion strength test.

The electric or electronic component encapsulating material of the present invention is a molded product obtained by injecting a resin or a resin composition which has been heated and kneaded and imparted fluidity into a mold set in an inside of a mold at a low pressure of 0.1 to 10 MPa, By wrapping and sealing the electric / electronic parts. In other words, since it is carried out at a very low pressure compared with injection molding at a high pressure of 40 MPa or more, which is conventionally used for plastic molding, it is difficult to break down electric and electronic parts which are sealed by an injection molding method and which are limited in heat resistance and pressure resistance It can be sealed without work. By appropriately selecting the sealing resin or the sealing resin composition, it is possible to obtain a sealing member having various durability against environmental loads and flame retardancy, which is resistant to environmental loads, against various polyester substrates, glass epoxy substrates, metals and the like. Hereinafter, the details of the embodiments of the invention will be described in order.

≪ Copolymerized polyester elastomer (X) >

The copolymer polyester elastomer (X) to be used in the present invention is a polyester elastomer having a hard segment mainly composed of a polyester segment and a soft segment composed mainly of a polycarbonate segment, a polyalkylene glycol segment and / or a polylactone segment Chemical structure. The polyester segment is preferably composed mainly of a polyester having a structure that can be formed by polycondensation of an aromatic dicarboxylic acid with an aliphatic glycol and / or an alicyclic glycol. The soft segment is preferably contained in an amount of not less than 20 wt% and not more than 80 wt%, more preferably not less than 30 wt% and not more than 70 wt%, and more preferably not less than 40 wt% and not more than 60 wt% .

The lower limit of the number average molecular weight of the copolymer polyester elastomer (X) used in the present invention is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. The upper limit of the number average molecular weight is not particularly limited, but is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less. If the number average molecular weight is too low, the resin composition for encapsulation may have insufficient hydrolytic resistance and the strength retention at high temperature and high humidity may be insufficient. If the number average molecular weight is too high, the melt viscosity of the resin composition becomes too high, Or the molding may become difficult.

The copolyester elastomer (X) used in the present invention is preferably a saturated polyester resin, and is preferably an unsaturated polyester resin having a minor amount of vinyl groups of 50 equivalents / 10 ⁶ g or less. When an unsaturated polyester having a high vinyl group concentration is used, crosslinking may occur at the time of melting, and the melt stability may be inferior.

The copolyester elastomer (X) used in the present invention may be a polyester having branches if copolymerized with a polycarboxylic acid or a polyol having three or more functionalities such as trimellitic anhydride and trimethylolpropane, if necessary.

In order to mold the copolymer polyester elastomer (X) used in the present invention without causing heat deterioration as much as possible, rapid melting at 210 to 240 ° C is required. Therefore, the upper limit of the melting point of the copolymer polyester elastomer (X) is preferably 210 ° C. Preferably 200 占 폚, and more preferably 190 占 폚. More preferably not less than 120 deg. C, particularly preferably not less than 140 deg. C, most preferably not less than 150 deg. C in consideration of handling performance at room temperature and normal heat resistance.

As a method for producing the copolymer polyester elastomer (X) to be used in the present invention, known methods can be used. For example, a polycarboxylic acid component and a polyol component to be described later are subjected to an esterification reaction at 150 to 250 DEG C, To 300 占 폚 to obtain a copolymer polyester elastomer. Alternatively, a transesterification reaction may be carried out at a temperature of 150 ° C to 250 ° C using a derivative such as a dimethyl ester of a polycarboxylic acid described later and a polyol component, and then subjected to a polycondensation reaction at 230 ° C to 300 ° C under reduced pressure to obtain a copolymer polyester elastomer Can be obtained.

Examples of the method for determining the composition and the composition ratio of the copolymer polyester elastomer (X) used in the present invention include ¹ H-NMR, ¹³ C-NMR, and poly (vinylidene fluoride), which are measured by dissolving a polyester resin in a solvent such as heavy chloroform. And a quantitative determination by gas chromatography measured after the methanolysis of the ester resin (hereinafter sometimes abbreviated as methanollisis-GC method). In the present invention, when a copolymer polyester elastomer (X) can be dissolved and a solvent suitable for ¹ H-NMR measurement is present, the composition and composition ratio are determined by ¹ H-NMR. In the case where there is no suitable solvent or when the composition ratio can not be determined only by ¹ H-NMR measurement, ¹³ C-NMR or methanollis-GC method is adopted or used in combination.

≪ Hard Segment of Copolymerized Polyester Elastomer (X) >

The hard segment of the copolymer polyester elastomer (X) of the present invention is preferably composed of a hard segment mainly composed of a polyester segment.

The acid component constituting the polyester segment is not particularly limited, but it is preferable that an aromatic dicarboxylic acid having 8 to 14 carbon atoms is contained in an amount of 50 mol% or more of the total acid component in order to improve the heat resistance of the copolymer polyester elastomer . The aromatic dicarboxylic acid having 8 to 14 carbon atoms is terephthalic acid and / or naphthalenedicarboxylic acid, which is highly reactive with glycol, and is preferable in view of polymerizability and productivity. More preferably at least 80 mol%, still more preferably at least 95 mol%, of the total acid component of terephthalic acid and naphthalene dicarboxylic acid with respect to the total acid component of the copolymer polyester elastomer, Is composed of terephthalic acid and / or naphthalene dicarboxylic acid.

Examples of other acid components constituting the polyester segment include aromatic dicarboxylic acids such as diphenyldicarboxylic acid, isophthalic acid and 5-sodium sulfoisophthalic acid, cyclohexanedicarboxylic acid, and tetrahydrophthalic anhydride. And dicarboxylic acids such as aliphatic dicarboxylic acids such as alicyclic dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimeric acid and hydrogenated dimeric acid. have. These dicarboxylic acid components are used within a range that does not significantly lower the melting point of the resin, and the copolymerization ratio thereof is less than 30 mol%, preferably less than 20 mol%, of the total acid component. As other acid components constituting the polyester segment, it is also possible to use a polycarboxylic acid having three or more functions such as trimellitic acid and pyromellitic acid. The copolymerization ratio of the trifunctional or higher polycarboxylic acid is preferably 10 mol% or less, more preferably 5 mol% or less, from the viewpoint of preventing gelation of the resin composition.

The aliphatic glycol or alicyclic glycol constituting the polyester segment is not particularly limited, but an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol is preferably contained in an amount of 50 mol% or more of the total glycol component, And more preferably from 8 to 8 carbon atoms. Examples of preferred glycol components include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like. 1,4-butanediol and 1,4-cyclohexanedimethanol are most preferable in view of a high-melting point design for improving the heat resistance of the polyester elastomer. As a part of the glycol component, a trifunctional or higher polyol such as glycerin, trimethylol propane or pentaerythritol may be used. From the viewpoint of preventing gelation of the resin composition, the content is preferably 10 mol% or less, more preferably 5 mol% or less .

The component constituting the polyester segment is preferably composed of a butylene terephthalate unit or a butylene naphthalate unit because the polyester elastomer has a high melting point and can improve the heat resistance and is particularly preferable in terms of moldability and cost performance Do.

≪ Soft segment of copolymer polyester elastomer (X) >

The soft segment of the copolymer polyester elastomer of the present invention is preferably composed of a soft segment mainly composed of a polycarbonate segment, a polyalkylene glycol segment and / or a polylactone segment. The copolymerization ratio of the soft segment is preferably 1% by mole or more, more preferably 5% by mole or more, and more preferably 10% by mole or more, based on 100% by mole of the total glycol component constituting the copolymer polyester elastomer (X) , And particularly preferably 20 mol% or more. Further, it is preferably 90 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less, particularly preferably 45 mol% or less. If the copolymerization ratio of the soft segment is too low, the melt viscosity of the resin composition of the present invention becomes high and the molding can not be performed at a low pressure, or the crystallization speed tends to be high, causing short shot. When the copolymerization ratio of the soft segment is too high, there is a tendency that the heat resistance of the sealing member of the present invention is insufficient.

The number average molecular weight of the soft segment is not particularly limited, but is preferably 400 or more, more preferably 800 or more. If the number average molecular weight of the soft segment is too low, flexibility can not be imparted, and there is a tendency that a stress load on the electronic substrate after sealing is increased. The number average molecular weight of the soft segment is preferably 5,000 or less, and more preferably 3,000 or less. If the number average molecular weight is too high, compatibility with other copolymerizable components tends to be poor, and copolymerization tends to occur.

As the polycarbonate segment used for the soft segment, those mainly composed of a polycarbonate structure in which an aliphatic diol residue having 2 to 12 carbon atoms is bonded by a carbonate group can be cited. An aliphatic diol residue having 4 to 12 carbon atoms is preferable and an aliphatic diol residue having 5 to 9 carbon atoms is particularly preferable in view of the flexibility and low temperature characteristics of the obtained polyester elastomer. The aliphatic diol residues may be used alone or in combination of two or more.

Specific examples of the polyalkylene glycol segment used in the soft segment include polyethylene glycol, polytrimethylene glycol, and polytetramethylene glycol. Most preferred is polytetramethylene glycol in terms of imparting flexibility and low melt viscosity.

Specific examples of the polylactone segment used in the soft segment include polycaprolactone, polyvalerolactone, polypropiolactone, polyundecaractone, and poly (1,5-oxetan-2-one).

≪ Polyester resin (A) >

The polyester resin (A) used in the present invention is a crystalline polyester resin in which a polyether diol is copolymerized, and is a kind of a copolymer polyester elastomer (X). By copolymerizing the polyether diol, it exhibits characteristics such as reduction of the melt viscosity, imparting flexibility, and imparting adhesion. The copolymerization ratio of the polyether diol is preferably 1% by mole or more, more preferably 5% by mole or more, and more preferably 10% by mole or more, based on 100% by mole of the total glycol component constituting the crystalline polyester resin (A) Or more, and particularly preferably 20 mol% or more. Further, it is preferably 90 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less, particularly preferably 45 mol% or less. If the copolymerization ratio of the polyether diol is too low, the melt viscosity tends to be high, which makes it impossible to form at low pressure, or the crystallization speed is high and short shot occurs. In addition, if the copolymerization ratio of the polyether diol is too high, there is a tendency to cause a problem of insufficient heat resistance. On the other hand, the number average molecular weight of the polyether diol is preferably 400 or more, more preferably 800 or more. If the number average molecular weight is too low, flexibility can not be imparted, and there is a tendency that a stress load on the electronic substrate after sealing tends to increase. The number average molecular weight of the polyether diol is preferably 5,000 or less, more preferably 3,000 or less. When the number average molecular weight is too high, compatibility with other components is poor, and there is a tendency that copolymerization can not be performed. Specific examples of the polyether diol include polyethylene glycol, polytrimethylene glycol, and polytetramethylene glycol, and polytetramethylene glycol is most preferable in terms of imparting flexibility and lowering the melt viscosity.

In the constituent components of the crystalline polyester resin (A) of the present invention, polyethylene terephthalate (hereinafter referred to as PET (polyvinylidene fluoride)), which is generally used as an engineering plastic by adjusting the composition ratio of the aliphatic component and / or the alicyclic component and the aromatic component, (Hereinafter sometimes abbreviated as " PBT "), and heat resistance comparable to that of the two-liquid curing type epoxy resin and a low melt viscosity, which are not present in a general crystalline polyester resin such as polybutylene terephthalate And can exhibit exothermic, moist, and cold and heat cycling properties. For example, in order to maintain a high heat resistance of 150 占 폚 or more, a copolymer polyester based on terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, naphthalene dicarboxylic acid and ethylene glycol, naphthalene dicarboxylic acid and 1,4- Is suitable. Particularly, since mold releasability due to rapid crystallization after molding is preferable in terms of productivity, it is preferable to use terephthalic acid with a high crystallinity and 1,4-butanediol, naphthalenedicarboxylic acid and 1,4-butanediol as main components .

It is preferable from the viewpoint of heat resistance that either or both of terephthalic acid and naphthalenedicarboxylic acid are contained as an acid component constituting the crystalline polyester resin (A). The copolymerization ratio is preferably 65 mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more when the total amount of terephthalic acid and naphthalene dicarboxylic acid is 100 mol% . If the total amount of terephthalic acid and naphthalene dicarboxylic acid is too low, the heat resistance required for electrical and electronic parts may be insufficient.

In addition, it is preferable that either or both of ethylene glycol and 1,4-butanediol be contained as the glycol component constituting the crystalline polyester resin (A) in view of maintaining the crystallinity at the time of copolymerization. The copolymerization ratio is preferably 40 mol% or more, more preferably 45 mol% or more, particularly preferably 50 mol% or more when the total amount of ethylene glycol and 1,4-butanediol is 100 mol% , And most preferably at least 55 mol%. When the total amount of ethylene glycol and 1,4-butanediol is too low, the crystallization rate is lowered, moldability is deteriorated such as mold releasability and molding time are prolonged, crystallinity is insufficient, and heat resistance is insufficient.

In the polyester resin (A) of the present invention, it is preferable that the base composition comprising the acid component and the glycol component, which imparts high heat resistance, is at least one selected from the group consisting of adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, Cycloaliphatic dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 4-methyl-1,2-cyclohexane dicarboxylic acid, dimer acid, Dicarboxylic acids such as 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, Hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl- Tricyclodecane dimethanol, neopentyl glycol hydroxypivalic acid ester, 1,9-nonanediol, 2-methyloctanediol, 1,10-dodecanediol, 2-butyl- Diol, polytetra Ethylene glycol, polyoxyethylene can use aliphatic or alicyclic glycols such as glycol as a copolymer component, there is a case to further improve the adhesion between the resin composition of the present invention.

The aliphatic and / or alicyclic dicarboxylic acids having 10 or more carbon atoms such as dimer acid and hydrogenated dimer acid and / or aliphatic and / or cycloaliphatic dicarboxylic acids having 10 or more carbon atoms such as dimer diol and hydrogenated dimer diol are added to the polyester resin (A) Or an alicyclic diol, the glass transition temperature may be lowered while maintaining a high melting point, so that compatibility between the heat resistance of the resin composition of the present invention and the adhesiveness to electrical and electronic parts can be further improved.

Further, it is preferable to use a polyalkylene glycol having a relatively high molecular weight represented by polyalkylene ether glycol such as aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms such as dimer acid or dimer diol and / or aliphatic or alicyclic diol having 10 or more carbon atoms and polytetramethylene glycol When a block-shaped segment composed of an aliphatic component is introduced, the resistance to hydrolysis is improved as the glass transition temperature of the polyester resin (A) is lowered as the ester group concentration is lowered, This important case is a more desirable policy. The term "durability in the cold / heat cycle" as used herein refers to the performance that peeling of the interface portion between an electronic component or the like having a different coefficient of linear expansion and a sealing resin or cracking of the sealing resin hardly occurs even when the temperature is raised or lowered several times between high temperature and low temperature. If the modulus of elasticity of the resin significantly increases during cooling, peeling and cracking are likely to occur. In order to provide a material resistant to cold and heat cycles, the glass transition temperature is preferably -10 DEG C or lower. More preferably -20 占 폚 or lower, even more preferably -40 占 폚 or lower, and most preferably -50 占 폚 or lower. The lower limit is not particularly limited. However, considering adhesion and blocking resistance, a temperature of -100 DEG C or more is realistic.

In the meantime, dimer acid is an aliphatic or alicyclic dicarboxylic acid (most of dimers contain trimers, monomers, and the like in a molar ratio of several mol%) generated by polymerization or unsaturated fatty acid dimerization by Diels-Alder reaction or the like, Quot; hydrogenated dimer acid " means a hydrogenated dimer acid in which hydrogen is added to the unsaturated bond portion of the dimer acid. The term "dimer diol" or "hydrogenated dimer diol" means the dimer acid or the two carboxyl groups of the hydrogenated dimer acid reduced to a hydroxyl group. Specific examples of the dimer acid or the dimer diol include Empol (registered trademark) or Sobamol (registered trademark) of Cognis, and Freepol of Unikemasa.

On the other hand, in the polyester resin (A) of the present invention, a small amount of an aromatic copolymerization component can also be used so far as the low melt viscosity is maintained. Examples of preferable aromatic copolymerization components include aromatic dicarboxylic acids such as aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, ethylene oxide adducts of bisphenol A, and propylene oxide adducts. In particular, by introducing an aliphatic component having a relatively high molecular weight such as dimer acid or dimer diol, good mold releasability due to rapid crystallization after molding may be obtained.

In order to impart long-term durability to the electrical and / or electronic parts encapsulating material, the ester group concentration of the polyester resin (A) is preferably 8000 equivalents / 10 ⁶ g in order to impart hydrolysis resistance against high temperature and humidity . The preferred upper limit is 7500 equivalents / 10 ⁶ g, more preferably 7000 equivalents / 10 ⁶ g. In order to ensure chemical resistance (gasoline, engine oil, alcohol, general-purpose solvent, etc.), the lower limit is preferably 1000 equivalents / 10 ⁶ g. A preferred lower limit is 1500 equivalents / 10 ⁶ g, more preferably 2000 equivalents / 10 ⁶ g. Here, the unit of the ester group concentration is represented by an equivalent number per 10 ⁶ g of the resin, and is a value calculated from the composition of the polyester resin and the copolymerization ratio thereof.

A block-like segment is copolymerized with an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms such as dimer acid, hydrogenated dimer acid, dimer diol and hydrogenated dimer diol and / or an aliphatic or alicyclic diol having 10 or more carbon atoms, When it is introduced into the polyester resin (A), it is preferably 2 mol% or more, more preferably 5 mol% or more when the total amount of the acid component and the total glycol component of the polyester resin (A) is 200 mol% , More preferably at least 10 mol%, and most preferably at least 20 mol%. The upper limit is 70 mol% or less, preferably 60 mol% or less, and more preferably 50 mol% or less, considering handling properties such as heat resistance and blocking.

The number average molecular weight of the polyester resin (A) of the present invention is preferably 3000 or more, more preferably 5000 or more, and further preferably 7000 or more. The upper limit of the number average molecular weight is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less. If the number average molecular weight is less than 3,000, the resin composition for sealing may be poor in hydrolysis resistance and in maintaining the strength and toughness under high temperature and high humidity. When the number average molecular weight is more than 50000, the melt viscosity at 220 캜 may be increased.

The polyester resin (A) of the present invention is preferably a saturated polyester resin containing no unsaturated group. If it is an unsaturated polyester, there is a possibility that crosslinking may occur at the time of melting, and the melt stability may be poor.

The polyester resin (A) of the present invention may also be a polyester having branches if copolymerized with polycarboxylic acids or polyols having three or more functionalities such as trimellitic anhydride and trimethylolpropane, if necessary.

In order to mold the polyester resin (A) without causing heat deterioration as much as possible, rapid melting at 210 to 240 ° C is required. Therefore, the upper limit of the melting point of the polyester resin (A) is preferably 210 ° C . Preferably 200 占 폚, and more preferably 190 占 폚. The lower limit may be 5 to 10 ° C or more higher than the heat resistance temperature required for the corresponding application. More preferably not less than 120 deg. C, particularly preferably not less than 140 deg. C, most preferably not less than 150 deg. C in consideration of handling performance at room temperature and normal heat resistance.

The polyester resin (A) of the present invention can be produced by a known method. For example, the dicarboxylic acid and the diol component are esterified at 150 to 250 ° C., By this addition, a desired polyester resin can be obtained. Alternatively, the polyester resin may be subjected to an ester exchange reaction at 150 ° C to 250 ° C using a derivative such as the dimethyl ester of the dicarboxylic acid and a diol component, followed by polycondensation at 230 ° C to 300 ° C under reduced pressure to obtain the desired polyester resin Can be obtained.

Examples of the method for determining the composition and composition ratio of the polyester resin (A) in the present invention include ¹ H-NMR or ¹³ C-NMR, which is measured by dissolving a polyester resin in a solvent such as chloroform, And a quantitative determination by gas chromatography (hereinafter abbreviated as methanollisis-GC method) which is measured after Nolisis. In the present invention, when a polyester resin (A) is soluble and a solvent suitable for ¹ H-NMR measurement is present, the composition and composition ratio are determined by ¹ H-NMR. In the case where there is no suitable solvent or when the composition ratio can not be determined only by ¹ H-NMR measurement, ¹³ C-NMR or methanollis-GC method is adopted or used in combination.

≪ Brominated epoxy resin (B1) and non-brominated epoxy resin (B2)

The brominated epoxy resin (B1) used in the resin composition of the present invention is an epoxy resin having an average of at least 1.1 glycidyl groups in the molecule and at least one bromine atom. For example, brominated bisphenol A diglycidyl ether, brominated novolak glycidyl ether and the like. In addition, glycidyl bromide ester type, alicyclic or aliphatic brominated epoxide, and the like can be given. Among them, in order to impart high adhesion and flame retardancy to electric and electronic parts, it is preferable that the copolymerizable polyester elastomer (X) or the polyester resin (A) has good compatibility. The number average molecular weight of the brominated epoxy resin (B1) is preferably in the range of 100 to 10000. When the number average molecular weight is less than 100, the encapsulating composition for electrical and electronic parts is easily softened, If it is 10000 or more, compatibility with the polyester resin (A) or the polyester resin (A) is lowered, and adhesion and flame retardancy may be impaired. Further, by using in combination with the non-brominated epoxy resin (B2) shown below, further improvement in adhesiveness can be expected and the bleed-out of the brominated epoxy resin (B1) from the encapsulant composition for electric and electronic parts is suppressed.

The brominated epoxy resin (B2) to be used in the resin composition of the present invention is preferably an epoxy resin having an average number of glycidyl groups in the molecule of from 450 to 40000 and a number average molecular weight of from 450 to 40000. Examples of the non-brominated epoxy resin (B2) include glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether and novolak glycidyl ether, hexahydrophthalic acid glycidyl ester, dimer acid Glycidyl ester type such as glycidyl ester, triglycidyl isocyanurate, glycidyl hydantoin, tetraglycidyl diaminodiphenyl methane, triglycidyl paraminophenol, triglycidyl methaminophenol, Glycidyl amines such as diglycidyl aniline, diglycidyl toluidine, tetraglycidyl methaxylenediamine, diglycidyl tribrom aniline, and tetraglycidylbisaminomycyclohexane, or 3,4-epoxy Alicyclic or aliphatic epoxides such as cyclohexylmethyl carboxylate, epoxidized polybutadiene, and epoxidized soybean oil. In order to exhibit high adhesion to electric and electronic components in the encapsulant composition for electrical and electronic parts of the present invention, compatibility with the copolymer polyester elastomer (X) or the polyester resin (A) as the non-brominated epoxy resin (B2) It is desirable to choose good ones. The number average molecular weight of the non-brominated epoxy resin (B2) is preferably 450 to 40000. If the number average molecular weight is less than 450, the adhesive agent composition tends to be very soft and may have poor mechanical properties. When the number average molecular weight is 40,000 or more, compatibility with the copolymer polyester elastomer (X) or the polyester resin (A) Thereby adversely affecting adhesion.

In the present invention, by mixing the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) in the resin composition for encapsulation, it is possible to obtain good initial adhesion and close adhesion to a high- It is possible to soften the flame retardant while imparting excellent properties such as durability.

The brominated epoxy resin (B1) is excellent in not only the effect as a flame retardant but also the stress relaxation effect due to the retardation of crystallization of the polyester resin (A), the effect of relaxation of the polyester resin elastomer (X) ) As a compatibilizing agent, and furthermore, exhibits an effect of improving the wettability to a substrate by the introduction of a functional group.

The use of the brominated epoxy resin (B1) in combination with the brominated epoxy resin (B1) can suppress the bleed out of the brominated epoxy resin (B1) from the resin composition for electric and electronic part encapsulation, and the copolymerized polyester elastomer ) Or a polyester resin (A) as a compatibilizing agent between the crystalline polyester resin (A) and the polyolefin resin (C), and furthermore, the effect of improving the wettability to the substrate by the introduction of a functional group Can be further added.

The total amount of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) in 100 parts by mass of the copolymer polyester elastomer (X) or the polyester resin (A) Is preferably 5 to 100 parts by mass. When the total amount of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) is less than 5 parts by mass, the stress relaxation effect due to the retardation of crystallization tends to be weak, and the polyolefin resin (C) The function as a compatibilizing agent of the present invention tends to become weak. When the total amount of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) is 100 parts by mass or more, the productivity of the resin composition is poor, and the properties such as the heat resistance of the sealing body may be poor.

Use of a brominated epoxy resin (B2) having a common chemical structure with the brominated epoxy resin (B1) tends to increase the bleed-out inhibiting effect of the brominated epoxy resin (B1), and is more preferable. For example, when a brominated bisphenol A type epoxy resin is used as the component (B1), it is preferable to use a bisphenol A type epoxy resin as the component (B2) and use a novolak type brominated epoxy resin as the component (B1) , It is preferable to use a novolak type epoxy resin as the component (B2). The blending ratio of the non-brominated epoxy resin (B2) is preferably 10 wt% or more and 50 wt% or less with respect to the brominated epoxy resin (B1). If the blending ratio of the non-brominated epoxy resin (B2) is 10 wt% or less, the bleed-out inhibiting effect may not be exhibited. If the blending ratio is 50 wt% or more, flame retardancy may not be exhibited.

≪ Polyolefin resin (C) >

In the present invention, mixing the polyolefin resin (C) in the resin composition for sealing exhibits excellent properties such as good adhesiveness and close contact durability against high temperature and light environmental loads when sealing electric and electronic parts. It is considered that the polyolefin resin (C) exerts the strain energy reducing effect by crystallization and enthalpy relaxation of the copolymer polyester elastomer (X) or the polyester resin (A). The blending amount of the polyolefin resin (C) in the present invention is 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the copolymer polyester elastomer (X) or the polyester resin (A). When the amount of the polyolefin resin (C) is less than 0.5 part by mass, it is difficult to relax the strain energy due to crystallization or enthalpy relaxation of the copolymer polyester elastomer (X) or the polyester resin (A), so that the adhesion strength tends to decrease . When the polyolefin resin (C) is blended in an amount of 50 parts by mass or more, on the other hand, adhesion and resin properties tend to be lowered. In addition, when the copolymerized polyester elastomer (X) or the polyester resin (A) and the polyolefin resin (C) undergo macro phase separation, the elongation at break is lowered and a smooth surface can not be obtained, .

The polyolefin resin (C) used in the present invention preferably has a density of 0.75 g / cm3 or more and less than 0.91 g / cm3. By using such an ultra-low density polyolefin, the polyolefin resin (C) can be easily finely dispersed and mixed with respect to the originally incompatible copolymer polyester elastomer (X) or the polyester resin (A) A homogeneous resin composition can be obtained by a general kneading apparatus such as a single screw extruder or a twin screw extruder without requiring a special kneading apparatus. In addition, the low density and low crystallinity also function properly to alleviate the residual stress in the injection molding that occurs in the co-extruded polyester elastomer (X) or the crystalline polyester resin (A) over time, And exhibits desirable characteristics such as a long-term close contact durability and a reduction in stress caused by an environmental load. As the polyolefin resin (C) having such properties, polyethylene and an ethylene copolymer are particularly preferable because they are easily available, inexpensive, and do not adversely affect the adhesion to a metal or a film. Specific examples thereof include low density polyethylene, ultra low density polyethylene, linear low density polyethylene, ethylene propylene elastomer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate- maleic anhydride terpolymer, - maleic anhydride terpolymer, ethylene-methacrylic acid glycidyl copolymer, ethylene-vinyl acetate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate-glycidyl methacrylate terpolymer It is a combination.

It is preferable that the polyolefin resin (C) does not contain a polar group capable of reacting with a polyester resin (A) such as a carboxyl group or a glycidyl group. When the polar group is present, the compatibility with the copolymer polyester elastomer (X) or the polyester resin (A) is changed, and the strain energy at the time of crystallization of the copolymer polyester elastomer (X) or the polyester resin (A) There is a case that can not be. Generally, polyolefins having a polar group tend to have higher compatibility with polyester resins than polyolefins having no polar group. In the present invention, the higher the compatibility, the lower the adhesiveness with time tends to become larger.

<Phenol resin and / or phenol-modified alkylbenzene resin (D)>

The component (D) used in the present invention is a phenol resin (D1) and / or a phenol-modified alkylbenzene resin (D2). In the resin composition for electric / electronic parts of the present invention, either or both of the phenol-modified alkylbenzene resin (D2) and / or the phenol resin (D1) can be used. The blending ratio of the phenol-modified alkylbenzene resin (D2) and / or the phenol resin (D1) is preferably 0 to 50 parts by mass relative to 100 parts by mass of the polyester resin. The component (D1) and the component (D2) are not essential components, but the addition of the component (D1) can reduce the bleeding-out of the brominated epoxy resin (B1) and / The effect of improving the adhesion may be exhibited. In particular, when the chemical structures of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) are inadequate in common, the bleed-out inhibiting effect tends to be remarkably exerted.

The phenol-modified alkylbenzene resin (D2) used in the resin composition of the present invention is obtained by modifying an alkylbenzene resin with phenol and / or alkylphenol, and preferably has a number average molecular weight of 450 to 40,000. The phenol-modified alkylbenzene resin (D2) can be prepared by, for example, reacting an alkylbenzene such as xylene or mesitylene with an aldehyde such as formaldehyde in the presence of an acidic catalyst to prepare an alkylbenzene resin, Aldehyde. &Lt; / RTI &gt; The phenol-modified alkylbenzene resin (D2) is preferably an alkylphenol-modified xylene resin or an alkylphenol-modified mesitylene resin. The xylene resin is a polymerizable composition having a basic structure in which a xylene structure is crosslinked with a methylene group or an ether bond. Typically, it can be obtained by heating metaxylene and formaldehyde in the presence of sulfuric acid. The mesitylene resin is a high molecular weight composition having a basic structure in which the mesitylene structure is crosslinked with a methylene group or an ether bond. Typically, it can be obtained by heating mesitylene and formaldehyde in the presence of sulfuric acid. The xylene resin and mesitylene resin are typical of alkylbenzene resins. The phenol-modified alkylbenzene resin (D2) of the present invention preferably has a hydroxyl group value of 100 equivalents / 10 ⁶ g or more, more preferably 1,000 equivalents / 10 ⁶ g or more, more preferably 5000 equivalents / 10 ⁶ g or more Do. Further, it is preferably 20000 equivalents / 10 ⁶ g or less, more preferably 15000 equivalents / 10 ⁶ g or less. If the hydroxyl value is too low, the adhesion to the aluminum material tends to deteriorate. If the hydroxyl value is too high, the water absorbency becomes high and the insulating property tends to be lowered. On the other hand, the hydroxyl value referred to here is measured by JIS K 1557-1: 2007A method.

The phenol resin (D1) used in the resin composition of the present invention is a resin obtained by the reaction of phenols and aldehydes, and may be a novolac phenol resin or a cresol phenolic resin, and has a number average molecular weight of 450 to 40,000 . Examples of the phenols which can be used as a starting material for the phenol resin include phenols such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol and 2,5- Functional phenols such as phenol, phenol, m-cresol, m-ethylphenol, 3,5-xylenol and m-methoxyphenol, quaternary phenols such as bisphenol A and bisphenol F, Or a combination of two or more of them. As the formaldehyde used for the production of the phenol resin, one or more of formaldehyde, paraformaldehyde, trioxane and the like may be used in combination. Other examples include phenol-modified resins such as phenol aralkyl and phenol-modified xylene resins. Among them, in order to exhibit particularly high adhesion, it is preferable that the polyester resin (A) has good compatibility with the polyester resin (A). In order to obtain a phenol resin having good compatibility with the copolyester elastomer (X) or the polyester resin (A), it is preferable to have a hydroxyl value near to the melt viscosity. The phenol resin (D1) of the present invention preferably has a hydroxyl value of 100 equivalents / 10 ⁶ g or more, more preferably 500 equivalents / 10 ⁶ g or more, and still more preferably 1,000 equivalents / 10 ⁶ g or more. Further, it is preferably 10,000 equivalents / 10 ⁶ g or less, more preferably 5000 equivalents / 10 ⁶ g or less. If the hydroxyl value is too low, the adhesion to the aluminum material tends to deteriorate. If the hydroxyl value is too high, the water absorbency becomes high and the insulating property tends to decrease. On the other hand, the hydroxyl value referred to here is measured by JIS K 1557-1: 2007A method.

&Lt; Resin composition for sealing electric / electronic parts &

The resin composition for sealing an electrical and / or electronic part of the present invention comprises a crystalline polyester resin (A), a brominated epoxy resin (B1), a non-brominated epoxy resin (B2) in which a copolymerized polyester elastomer (X) And a polyolefin resin (C), and having a water content of not more than 0.1%, heated to 220 캜 and subjected to a pressure of 1 MPa, and extruded from a die having a pore diameter of 1.0 mm and a thickness of 10 mm to have a melt viscosity of 5 dPa · s or more and 3000 dPa · s or less. 5 to 100 parts by mass of the total amount of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) relative to 100 parts by mass of the copolymerized polyester elastomer (X) or the crystalline polyester resin (A) ) And 0.1 to 100 parts by mass of the phenol resin (D1) and / or the phenol-modified xylene resin (D2) and 0 to 50 parts by mass of the phenol resin (D1) and the non-brominated epoxy resin (B2) Or more and 50 mass% or less.

The resin composition for encapsulating electric / electronic parts of the present invention preferably has a melt viscosity at 220 캜 of 5 to 3000 dPa 하고, and further contains a copolymerized polyester elastomer (X), a crystalline polyester resin (A), a brominated epoxy resin (B1), the non-brominated epoxy resin (B2), the polyolefin resin (C) and the phenol resin (D1) and / or the phenol-modified xylene resin (D2). For example, increasing the copolymerization ratio of the polyether diol to be copolymerized with the crystalline polyester resin (A) and decreasing the molecular weight of the crystalline polyester resin (A) are effects of lowering the melt viscosity of the resin composition of the present invention , And the increase in the molecular weight of the crystalline polyester (A) tends to act in a direction to increase the melt viscosity of the resin composition of the present invention. Here, the melt viscosity at 220 캜 is a value measured as follows. That is, the resin composition for sealing was dried at a moisture content of 0.1% or less, and then heated at 220 占 폚 by a flow tester (model number CFT-500C) manufactured by Shimadzu Seisakusho Co., Ltd. to form a stable sealing resin composition, And a die having a diameter of 10 mm is passed at a pressure of 98 N / cm &lt; 2 &gt;. When a high melt viscosity of 3000 dPa · s or more is achieved, a high resin cohesive force and durability can be obtained. However, when sealing a component having a complicated shape, injection molding at a high pressure is required. The resin composition for sealing having a melt viscosity of not more than 1,500 dPa · s, preferably not more than 1,000 dPa · s, more preferably not more than 800 dPa · s is used, The excellent molded part can be obtained and the characteristics of the electric and electronic parts are not impaired. From the viewpoint of injecting the resin composition for sealing, it is preferable that the melt viscosity at 220 캜 is low. However, considering the adhesion property and cohesive force of the resin composition, the lower limit is preferably 5 dPa · s or more, more preferably 10 dPa · s or more, more preferably 50 dPa · s or more, and most preferably 100 dPa · s or more.

&Lt; Other components >

(A), a brominated epoxy resin (B1), a non-brominated epoxy resin (A), a brominated epoxy resin (B), and a copolymerized polyester elastomer (B) for the purpose of improving the adhesiveness, flexibility, durability, (X), (A), (B1), (B2) and (B2) of polyester, polyamide, polyolefin, epoxy, polycarbonate, acrylic, ethylene vinyl acetate, phenol and the like as components other than the polyolefin resin (B1), such as a resin other than (C), an isocyanate compound, a curing agent such as melamine, a filler such as talc or mica, a pigment such as carbon black or titanium oxide, or antimony trioxide or brominated polystyrene, none. The polyester resin (A) at that time is preferably contained in an amount of 40% by weight or more, more preferably 50% by weight or more, based on the entire composition. If the content of the copolymer polyester elastomer (X) or the polyester resin (A) is less than 40% by weight, the cohesive polyester elastomer (X) or the polyester resin (A) Durability, retention of retention, hydrolysis resistance and water resistance may be deteriorated.

When the electrical and electronic component encapsulant of the present invention is exposed to a high temperature and high humidity environment for a long period of time, it is preferable to add an antioxidant to the resin composition for encapsulating electric / electronic parts of the present invention. Examples of preferred antioxidants include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri Methyl-5-t-butylphenyl) butane, 1,1-bis (3-t- butyl- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid, pentaerythrityl tetrakis (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,3- Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di- (P-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphospiro [5.5] undecane, 3,9-bis Bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphospiro [5.5] undecane, tri (monononylphenyl) phosphite, (Nonylphenyl) ester phosphorous acid, 1,1,3-tris (2-methyl-4-thiophene) phosphate, dodecylphenylphosphite, isodecylphosphate, isodecylphenylphosphite, diphenyl 2-ethylhexylphosphite, dinonylphenylbis (2,4-di-t-butylphenyl) phosphite, pentaerythritolbis (2,4-di-t-butylphenylphosphite), ditridecylphosphite (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6- (2-t-butyl-5-methylphenol) bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl) (3-n-dodecylthiopropionate), bis (tridecyl) thiophenate, bis (trimethylsilyl) And the like, and they can be used singly or in combination. The addition amount is preferably 0.1 wt% or more and 5 wt% or less with respect to the total of the resin composition for encapsulation. If it is less than 0.1% by weight, the deterioration preventing effect may be insufficient. On the other hand, if it exceeds 5% by weight, adherence may be adversely affected.

&Lt; Manufacturing Method of Electrical and Electronic Parts Sealing Material &

The electrical and electronic parts encapsulating material of the present invention can be produced by heating and kneading the resin composition for encapsulating electric / electronic parts of the present invention and then injecting the resulting mixture into a mold having electric / electronic parts inserted therein. Here, the resin composition for encapsulating electric / electronic parts of the present invention may be one in which all or a part of constituent components are mixed and heated and kneaded just before the injection of the mold, even if the entire constituents of the resin composition are separately heated and kneaded beforehand.

The resin composition temperature and the resin composition pressure at the time of mold injection are not particularly limited, but when the resin composition temperature is not less than 130 ° C. and not more than 260 ° C. and the resin composition pressure is not less than 0.1 MPa and not more than 10 MPa, Do. For injection of the resin, for example, an applicator for screw-type hot-melt molding can be used. The type of the applicator for hot melt molding processing is not particularly limited, and for example, ST2 manufactured by Nordson Corporation of Germany, vertical extrusion molding machine manufactured by Imoto Seisakusho Co., Ltd., and the like.

Example

The following examples and comparative examples are provided to further illustrate the present invention, but the present invention is not limited by these examples. On the other hand, each measurement value described in the examples and comparative examples was measured by the following method.

<Measurement of Melting Point and Glass Transition Temperature>

5 mg of the sample to be measured was put into an aluminum pan by a differential scanning calorimeter "DSC220 type" manufactured by Seiko Denshi Kogyo Co., Ltd., and the lid was sealed by pressing. After holding for 5 minutes at 250 ° C, the sample was quenched with liquid nitrogen , And then from -150 ° C to 250 ° C at a heating rate of 20 ° C / min. The inflection point of the obtained curve was regarded as a glass transition temperature, and the endothermic peak was defined as a melting point.

&Lt; Measurement of ten point average roughness &

Using a Surf Test 600 manufactured by Mitsutoyo Co., Ltd., the measurement length was 5 mm at any 5 of the surfaces of the substrates 4 and 5 which were in contact with the sealing resin composition, and measured according to JIS B 0601-1994 Ten-point surface roughness was calculated. On the other hand, the following specifications were used for the stylus used for measurement.

Stylus Fuselage Material: Diamond

Stylus tip shape: 90 ° cone

Stylus tip curvature radius: 2 ㎛

<Adhesive Strength Test>

Preparation method of adhesion strength test piece

A substrate 4 (25 mm wide x 48 mm long x 2 mm thick) and a substrate 5 (25 mm wide x 70 mm long x 2 mm thick) made of FR-4 glass epoxy board NIKAPLEX manufactured by Nikkan Kogyo Co., The spacer 3 was provided together with the molding die 1 (inner dimensions of the mold: 100 mm wide × 100 mm long × 5 mm thick). Subsequently, the sealing resin composition was injected from the gate 2 using an applicator for screw-type hot melt molding (a vertical type low-pressure extrusion molding machine manufactured by Imoto Seisakusho Co., Ltd.), and injection molding was performed. The injection molding conditions were a molding resin temperature of 220 캜, a molding pressure of 3 MPa, a holding pressure of 3 MPa, a cooling time of 15 seconds, and an injection speed of 50%. Figs. 1 to 3 are schematic diagrams of a cross section of a mold (1), showing the state at the time when the injection of the resin composition for sealing is completed, and Fig. 2 is a sectional view taken along the line AA ' 2 and the CC 'cross section in Fig. 3 correspond to Fig. The molded product was released, and the sealing resin composition other than the overlapping portion between the flat plate 4 and the flat plate 5 was cut out to obtain a close adhesion strength test piece. Hereinafter, this test piece is referred to as a glass epoxy adhesion test piece. The glass epoxy adhesion test specimen has a structure in which a sealing resin composition having a thickness of 1 mm is filled and adhered to an overlapping portion (25 mm in width and 18 mm in length) of glass epoxy plates, and the adhesion area between the glass epoxy plate and the resin composition Is 25 x 18 = 450 mm &lt; 2 &gt;. On the other hand, the glass epoxy plate used herein had a ten-point average roughness of the surface of the adhesive portion within a range of 0.5 to 3 占 퐉.

The adhesion test piece was allowed to stand in an atmosphere of 23 DEG C and 50% RH for not less than 3 hours and not more than 100 hours, and then tensile was applied in the longitudinal direction of the test piece to give a shearing force. The tensile speed was set at 50 mm / min. The strength at the time of fracture per a close contact area (450 mm 2) was defined as the shear adhesion strength.

Evaluation standard

◎: shear adhesion strength 1.0 MPa or more

○: Shear adhesion strength Less than 1.0 MPa Less than 0.5 MPa

X: shear adhesion strength less than 0.5 MPa

<Melting Property Test>

Method for evaluating the melt viscosity of a resin and a resin composition for sealing

A resin or a sealing resin composition dried at a moisture content of 0.1% or less was charged into a cylinder at the center of the heating body set at 220 캜 using a flow tester (CFT-500C type) manufactured by Shimadzu Seisakusho Co., A load was applied to the sample through a plunger and the molten sample was extruded from a die (hole diameter: 1.0 mm, thickness: 10 mm) at the bottom of the cylinder at a pressure of 1 MPa and the falling distance and dropping time of the plunger were recorded, The viscosity was calculated.

<Low Pressure Moldability Test>

A flat plate (100 mm x 100 mm x 10 mm) made of a resin composition for encapsulation was formed by using a mold for plate molding and using ST-2 manufactured by Nordson as an applicator for hot melt molding processing. On the other hand, the gate position was taken as the center of a face of 100 mm x 100 mm.

Molding conditions: molding resin temperature 220 캜, molding pressure 3 MPa, holding pressure 3 MPa, cooling time 15 sec, injection speed 50%

Setting evaluation criteria

○: Fully charged, no sync mark

△: Charged without shot, but with sync mark

×: Short shot available

&Lt; Flame retardancy test &

According to the evaluation method of UL-94, flame retardancy of two types of flame-retardant test pieces of 0.8 mm thickness and 1.6 mm thickness was evaluated.

Molding condition of test specimen

Molding resin temperature 220 캜, molding pressure 10 MPa, holding pressure 10 MPa, cooling time 25 sec, injection speed 20 g / sec.

Evaluation standard

?: Both of the above two types of flame-retardant test pieces were V0, V1 or V2

X: Either or both of the two types of flame-retardant test pieces are not V0, V1 or V2

<Bleed-Out Test>

The test piece prepared in the same manner as in the above flame retardancy test was allowed to stand under an environment of 25 ° C × 50% RH for 2 months, visually checked for bleed-out, and then the flame retardancy was evaluated by the flame retardancy test method.

Evaluation standard

&Amp; cir &amp;: No bleed-out that can be confirmed by eyes at the time of 2 months, and flame retardancy after bleed-out test is &quot;

○: There is a bleed-out that can be confirmed by eyes at the time of 2 months, but the flame retardancy after the bleed-out test is "○"

X: There is a bleed-out which can be confirmed by eyes at the lapse of two months, and the flame retardancy after the bleed-out test is &quot;

&Lt; Production Example of Copolymerized Polyester Elastomer &

166 parts by mass of terephthalic acid, 180 parts by mass of 1,4-butanediol and 0.25 parts by mass of tetrabutyl titanate were added to a reaction can equipped with a stirrer, a thermometer and an outlet cooler, and esterification reaction was carried out at 170 to 220 ° C for 2 hours. After completion of the esterification reaction, 300 parts by mass of polytetramethylene glycol &quot; PTMG1000 &quot; (manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 1000 and 100 parts by mass of a hindered phenol-based antioxidant &quot; Irganox (registered trademark) 0.5 part by mass was added and the temperature was raised to 255 占 폚 while the inside of the system was slowly depressurized and the pressure was made to be 665 Pa at 255 占 폚 over 60 minutes. Then, a polycondensation reaction was also carried out at 133 Pa or less for 30 minutes to obtain a copolymer polyester elastomer A. This copolymer polyester elastomer A had a melting point of 165 캜 and a melt viscosity of 250 dPa..

The copolyester elastomers B to E were synthesized by the same method as the copolymer polyester elastomer A. Tables 1 and 2 show the respective compositions and physical properties.

The abbreviations in the table are as follows.

PTMG 1000: polytetramethylene ether glycol (number average molecular weight 1000), PTMG 2000: polytetramethylene ether glycol (number average molecular weight: 2000), TPA: terephthalic acid, NDC: naphthalene dicarboxylic acid, BD: 1,4-

&Lt; Production Example of Resin Composition for Electrical and Electronic Component Sealing >

The resin composition 1 for sealing electric and electronic parts was prepared by mixing 100 parts by mass of the copolymer polyester elastomer A, 30 parts by mass of the polyolefin resin A, 30 parts by mass of the brominated epoxy resin A and 20 parts by mass of the non-brominated epoxy resin A , And melt-kneaded at a die temperature of 220 占 폚 using a twin-screw extruder. The sealing resin compositions 2 to 22 were prepared by the same method as the sealing resin composition 1. The compositions and physical properties of the respective compounds are shown in Tables 3 to 6.

The components used in Tables 3 to 6 are as follows.

Polyolefin Resin A: EXCELEN (registered trademark) VL EUL731, manufactured by Sumitomo Chemical Co., Ltd., alpha -olefin copolymerized very low density polyethylene, density 0.90.

Polyolefin resin B: Admer (registered trademark) SF-600, manufactured by Mitsui Chemicals, Inc., adhesive polyolefin, density 0.88.

Polyolefin resin C: Hygex (registered trademark) 2100J, high density polyethylene manufactured by Mitsui Chemicals, Inc., density 0.93.

Brominated epoxy resin A: BREN-S, brominated novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)

Brominated epoxy resin B: JER5050, bisphenol A bromide type epoxy resin manufactured by Mitsubishi Chemical Corporation

Non-brominated epoxy resin A: YDCN-704A, novolak type epoxy resin (trade name, manufactured by Shinnitetsu Kagaku Co., Ltd.)

Brominated epoxy resin B: JER1007K, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin

Non-brominated epoxy resin C: YD-017, bisphenol A type epoxy resin manufactured by Shinnitetsu Kagaku Co., Ltd.

Phenol-modified alkylbenzene resin A: HP-150, manufactured by Mitsubishi Gas Kagaku Co., Ltd.

Phenol resin A: EP4020, manufactured by Asahi Yuki Kaisha K.K., cresol novolak type phenol resin

Example 1

<Adhesion Strength Test>, <Bleeding-out Test>, <Low-Pressure Moldability Test> and <Flame Retardancy Test> were conducted using the sealing resin composition 1 as the sealing resin composition. In the < melting characteristic test >, it was 554 dPa · s and showed good melting characteristics. &Lt; Adhesion strength test > The initial adhesion strength to the glass epoxy-epoxy-adhered test piece was 1.3 MPa. The flame retardancy after the bleed-out test is maintained at V2 or higher. The < low-pressure moldability test > indicates that the flame retardancy after the bleed- Good results were obtained for all items. The evaluation results are shown in Table 3.

Examples 2 to 17

<Bonding strength test>, <Bleeding-out test>, <Low-pressure moldability test>, and <High-pressure moldability test> were carried out in the same manner as in Example 1 using the sealing resin compositions 2 to 17 as the resin composition for sealing. Flame Retardancy Test &gt; The evaluation results are shown in Tables 3 to 5.

Comparative Example 1

<Bonding strength test>, <Bleeding-out test>, <Low-pressure moldability test>, <Flame retardancy test>, and the like were carried out in the same manner as in Example 1 using the sealing resin composition 16 as the sealing resin composition . In the < melting characteristic test >, it was 554 dPa · s, and also in the <adhesion strength test>, the adhesive strength to the glass epoxy plate was good at 1.0 MPa. The <Flame Retardation Test> was also satisfactory in terms of V2, but in the <Bleed-out Test>, the bleed-out was confirmed as seen from the evaluation result and NG was obtained.

Comparative Examples 2 to 5

<Bonding strength test>, <Bleeding-out test>, <Low-pressure moldability test>, and <High-pressure moldability test> were carried out in the same manner as in Example 1 using the sealing resin compositions 18 to 22 as the resin composition for sealing. Flame Retardancy Test &gt; The evaluation results are shown in Table 6.

Examples 1 to 17 satisfied the claims and all of the results of <melt characteristics test>, <adhesion strength test>, <bleed out test>, <low pressure moldability test> and <flame retardancy test> were all good. On the other hand, Comparative Example 1 was out of the scope of the present invention because the non-brominated epoxy resin was not included, and the result of < bleeding-out test > Further, Comparative Examples 2 and 5 were outside the scope of the present invention because brominated epoxy resin was not included, and the flame retardancy test was poor in HB. Comparative Example 3 was out of the scope of the present invention because of a high melt viscosity, and the low-pressure moldability was poor. Comparative Example 4 was out of the scope of the present invention because the non-brominated epoxy resin was not contained in the same manner as in Comparative Example 1, and was inferior to HB in flammability test.

INDUSTRIAL APPLICABILITY The resin composition for encapsulating electric / electronic parts of the present invention can provide flame-retardant electrical and electronic parts encapsulant having no fill-up property at a practical level and no bleeding-out of flame retardant while maintaining adhesiveness between the encapsulant and electric / And is useful as an encapsulant used for sealing various electronic parts such as various connectors for use in automobiles, communications, computers, home appliances, harnesses or electronic parts, switches having printed boards, sensors, and the like.

1: mold, 2: gate, 3: spacer, 4, 5: substrate, 6: resin composition

Claims (7)

(B1), a non-brominated epoxy resin (B2), and a polyolefin resin (C), and dried at a moisture content of 0.1% or less, heated to 220 캜 and subjected to a pressure of 1 MPa , hole diameter 1.0 mm, the melt viscosity is 5 dPa · s or more or less 3.0 × 10 ³ dPa · s electrical and electronic parts encapsulating resin composition when extruded from the die having a thickness of 10 mm. (A), a brominated epoxy resin (B1), a non-brominated epoxy resin (B2) and a polyolefin resin (C) in which a polyether diol is copolymerized and dried at a moisture content of 0.1% And a melt viscosity of not less than 5 dPa · s and not more than 3000 dPa · s when extruded from a die having a pore diameter of 1.0 mm and a thickness of 10 mm by heating and applying a pressure of 1 MPa. The resin composition for sealing electric / electronic parts according to claim 1 or 2, wherein both of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) are bisphenol A type or novolac type epoxy resin. The thermoplastic resin composition according to any one of claims 1 to 3, wherein 100 parts by mass of the copolymer polyester elastomer (X) or the crystalline polyester resin (A), the total amount of the brominated epoxy resin (B1) and the non-brominated epoxy resin (B2) Wherein the non-brominated epoxy resin (B2) is contained in an amount of 10 to 50% by mass of the brominated epoxy resin (B1) in an amount of 5 to 100 parts by mass and the polyolefin resin (C) in an amount of 0.1 to 100 parts by mass, / RTI &gt; The resin composition for sealing electric / electronic parts according to any one of claims 1 to 4, further comprising a phenol resin and / or a phenol-modified alkylbenzene resin (D). A resin composition according to any one of claims 1 to 5, which is heated and kneaded, to a mold having electric and electronic parts inserted therein at a resin composition temperature of not less than 130 ° C and not more than 260 ° C, and a resin composition pressure of not less than 0.1 MPa 10 MPa or less. An electrical and electronic parts sealing body sealed with the resin composition according to any one of claims 1 to 5.

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